RU2560434C2 - Epoxy resin-based composition - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to an epoxy resin-based composition. The composition includes epoxy resin, a polyol and a carboxamide compound, where the carboxamide compound has the formula NH-CO-R, where R is 1) -NRR, 2) an alkyl having 1-10 carbon atoms and optionally including 1-3 hydroxyl and/or ether groups 3) phenyl or 4) tolyl, where Rand Rare independently selected from a hydrogen atom, hydroxy, phenyl, tolyl and alkyl, having 1-6 carbon atoms and optionally including a hydroxy- and/or ether group, and a mixture of said compounds, and where the number of hydroxyl equivalents per epoxide equivalent is 0.02-100 and preferably 0.03-50 and most preferably 0.05-10, and the number of carboxamide equivalents per epoxide equivalent is 0.0005-1 and preferably 0.005-0.7 and most preferably 0.01-0.5. A curable composition for producing a polyurethane-polyisocyanate material, which can be obtained by combining and mixing said epoxy resin-based composition and an aromatic polyisocyanate-based composition, which includes a polyisocyanate, lithium halide and urea compound, where the number of lithium halide moles per isocyanate equivalent is in the range of 0.0001-0.04, and the number of urea equivalents + biuret per isocyanate equivalent is in the range of 0.0001-0.4. The invention also relates to use of said carboxyamide compound to prolong the shelf life of the curable polyisocyanate-based composition.EFFECT: obtaining an epoxy resin-based composition for producing a curable composition which includes polyisocyanate.15 cl, 4 tbl

Description

The present invention relates to an epoxy resin composition and a curable composition obtained by combining said epoxy resin composition with a polyisocyanate composition. In addition, the present invention relates to a method for producing said epoxy resin composition and said curable composition. The present invention also relates to a method for producing a polyurethane-polyisocyanurate material based on the interaction of the curable composition, and to a polyurethane-polyisocyanurate material obtained by reaction in the curable composition.

Not so long ago, a curable composition was proposed having a viability time of up to 17 hours, which includes polyisocyanate, lithium halide, a urea compound and an epoxy resin, see PCT / EP2010 / 054492. The urea compounds used in PCT / EP2010 / 054492 are obtained by reacting polyisocyanates (R ₁ -NCO) with amines (R ₂ -NH ₂ ) and are called urea compounds and have the following structure R ₁ -NH-CO-NH-R ₂ , both radicals R ₂ and R ₃ are not a hydrogen atom.

Surprisingly, the inventors have found that the cure composition's viability retention time can be significantly improved, up to 300 hours or more, by using an epoxy resin composition that includes a compound that contains a carboxamide group having the structure —CO— NH ₂ without adversely affecting the subsequent cure of the curable composition.

Therefore, the present invention relates to an epoxy resin composition comprising an epoxy resin, a monohydroxy alcohol and / or a polyol and a compound comprising a carboxamide group, wherein the number of hydroxyl equivalents per epoxy equivalent is 0.02-100 and preferably 0.03-50 and most preferably 0.05-10, and the number of carboxamide equivalents per epoxy equivalent is 0.0005-1 and preferably 0.005-0.7 and most preferably 0.01-0.5.

Further, the present invention relates to a method for producing this epoxy resin composition, wherein a mixture of a monohydric alcohol and / or polyol and a compound comprising a carboxamide group is combined and mixed with an epoxy resin. The relative amounts of the ingredients are selected so that the epoxy resin composition includes these ingredients in the above amounts.

The present invention also relates to a curable composition obtained by combining and mixing a polyisocyanate-based composition comprising a polyisocyanate, lithium halide and a urea compound having an average molecular weight of 500-15000 and optionally including biuret groups, and an epoxy resin composition as defined above, where the number of moles of lithium halide per equivalent of isocyanate is in the range of 0.0001-0.04, the number of equivalents of urea + biuret per equivalent of isocyanate is in the range of 0.0001-0.4, and the number of epoxy equivalents per equivalent of isocyanate lies in the range of 0.003-1.

The present invention also relates to a method for producing a polyurethane-polyisocyanurate material based on the interaction of the above curable composition at an elevated temperature and to a polyurethane-polyisocyanurate material obtained in this way.

Finally, the present invention relates to the use of a compound that contains a carboxamide group having the structure —CO — NH ₂ to improve the life time of the curable polyisocyanate-based composition.

The use of lithium chloride and compounds comprising urea groups is disclosed by Sheth, Aneja and Wilkes in Polymer 45 (2004) 5979-5984. They studied the effect of the degree of hydrogen binding as an intermediary on the possibility of long-term bonding and permeability of the hard segmental phase in model tri-segment oligomeric polyurethanes using LiCl as a molecular sample.

In US Pat. No. 5,086,150, an isocyanate-terminated prepolymer is reacted with a diamine in the presence of a sufficiently high amount of LiCl to give a polymer solution that is stable for at least two days. At the beginning of the reaction, the number of moles of lithium chloride per equivalent of isocyanate is quite high; lithium chloride is used as a solubilizer. At the beginning of the reaction, the composition is not stable and does not contain urea, and at the end of the reaction it is an elastomer, and not an isocyanate-based composition. The resulting product is a polymer solution used to obtain filaments and films.

The use of isocyanates and epoxides together with LiCl is disclosed in Russian Chemical Reviews 52 (6) 1983, 576-593. The nature of the catalyst affects the course of the reaction. In the presence of metal halides, an activated complex forms, which ultimately gives oxazolidone. One of the adverse reactions is the formation of isocyanurate rings, which decompose to oxazolidone when treated with epoxides. In addition, it was disclosed in this publication that epoxides are capable of cleaving urea bonds to form oxazolidones.

US Pat. No. 4,658,007 provides a process for preparing an oxazolidone-containing polymer using an antimony iodide catalyst by reacting a polyisocyanate and a polyepoxide.

US 5326833 discloses a composition comprising a polyisocyanate, an epoxide and a catalyst consisting of a solution of an alkali metal halide, such as LiCl, in a polyoxyalkylene compound. These compositions are able to easily gel at a temperature between 0 ° C and 70 °.

Juan et al. Journal of East China University of Science and Technology, Vol.32, No. 11, 2006, 1293-1294, examines the effect of LiCl on the morphology of the structure and properties of polyurethane urea. It is shown that the viscosity of polyurethane urea solutions first decreases and then increases. Polyurethane urea was obtained by the reaction of polyepoxypropanoglycol and isophorondiisocyanate with an excess of polyisocyanate.

In US Pat. No. 3,571,039, acylated urea polyisocyanates are prepared by reacting an organic diisocyanate with an organic monocarboxylic acid. These polyisocyanates are used in the process of producing polyurethanes, especially when small amounts of branching are desired.

US Pat. No. 3,970,600 discloses stable solutions of isocyanurate-polyisocyanates containing amide and / or acylurea groups. They avoid the deposition of small or coarse crystalline solids in polyisocyanates, including isocyanurate groups. First, the polyisocyanate is reacted with the polybasic carboxylic acid to produce a polyisocyanate with amide and / or substituted acylurea groups. Then this polyisocyanate is trimerized to form isocyanurate-polyisocyanate, and this conversion is terminated by the addition of acid.

In JP 2-110123, an aliphatic diisocyanate is trimerized to produce polyisocyanates that have an isocyanurate structure using a catalyst and a deactivation agent as soon as the desired degree of conversion is achieved. The decontamination agent has the structure —CO — NH ₂ or —SO — NH ₂ and may be urea, methyl urea, 1,1-dimethyl urea, phenyl carbamate, ethyl carbamate or butyl carbamate. Then the deactivated catalyst, excess diisocyanate and the solvent, if used, are removed. When using this decontamination agent, a polyisocyanate comprising a polyisocyanurate structure exhibits a lower degree of discoloration.

WO 2008/068198 and US Patent 2010/0022707 disclose a process for producing an oligomerized polyisocyanate using a catalyst, wherein a deactivator is used as soon as the desired conversion is achieved, followed by removal of the polyisocyanate that has not undergone the conversion. The deactivator may be selected from urea and compounds containing urea, among others.

EP 585835 discloses a process for preparing mixtures of isocyanurate and a polyisocyanate containing urethane groups, by partial cyclization of diisocyanates in the presence of a trimerization catalyst, by deactivating the trimerization catalyst when the desired conversion is achieved, and then reacting the formed polyisocyanate containing isocyanurate groups with hydroxyl compounds separation of monomeric diisocyanate.

In the context of the present invention, the following terms have the following meanings:

1) isocyanate index or NCO index or index:

the ratio of NCO groups to hydrogen atoms chemically active to isocyanate present in the composition is given in percent:

([NCO] × 100) / [active hydrogen] (%)

In other words, the NCO index reflects the percentage of isocyanate actually used in the composition, relative to the amount of isocyanate theoretically required to interact with the amount of hydrogen reactive to isocyanate used in the composition.

You can see that the isocyanate index, as used in this document, is considered from the point of view of the real polymerization process to obtain a material comprising an ingredient based on isocyanate and ingredients chemically active to isocyanate. Any isocyanate groups consumed in the preliminary step to produce modified polyisocyanates (including these derivative isocyanates called prepolymers in the art) or any active hydrogen atoms absorbed in the preliminary step (for example, reacted with isocyanate to produce modified polyols or polyamines) are not accepted attention when calculating the isocyanate index. Only free isocyanate groups and free hydrogen atoms reactive to isocyanate (including those that belong to water, if used) that are present at the stage of real polymerization are taken into account.

2) The expression "chemically active hydrogen atoms" used in this document to calculate the isocyanate index refers to the total number of active hydrogen atoms in the hydroxyl and amine groups contained in the reaction compositions; this means that in order to calculate the isocyanate index in a real polymerization process, it is believed that one hydroxyl group includes one chemically active hydrogen atom, one primary amine group includes one chemically active hydrogen atom, and one water molecule contains two chemically active hydrogen atoms.

3) Reaction system: a combination of components, where the polyisocyanates are kept in one or more containers separate from the chemically active components to the isocyanate.

4) The term “average nominal hydroxyl functionality” (or “functionality” for short) is used herein to mean the number average functionality (number of hydroxyl groups per molecule) of a polyol or polyol composition, provided that it is number average functionality (number of active hydrogen atoms per the molecule) of the initiator (s) used in the process of obtaining it, although in practice it will often be slightly less due to some unsaturation of the end groups.

5) The term "average" refers to the number average, unless otherwise indicated.

The epoxy resin used in the epoxy resin composition of the present invention is preferably selected from any epoxy resin that is liquid at 20 ° C-25 ° C.

Examples of epoxy resins are as follows:

I) Polyglycidyl and poly (β-methylglycidyl) esters obtained by the reaction of a compound containing at least two carboxyl groups in the molecule, and, respectively, epichlorohydrin and β-methylepichlorohydrin. The reaction proceeds appropriately in the presence of bases.

Aliphatic polycarboxylic acids can be used as compounds containing at least two carboxyl groups in the molecule. Examples of these polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dimerized or trimerized linoleic acid.

However, cycloaliphatic polycarboxylic acids, such as, for example, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid, can also be used.

In addition, aromatic polycarboxylic acids can be used, such as, for example, phthalic acid, isophthalic acid or terephthalic acid.

II) Simple polyglycidyl or poly (β-methylglycidyl) esters obtained by the reaction of a compound containing at least two free alcohol hydroxyl groups and / or phenolic hydroxyl groups with epichlorohydrin or β-methylepichlorohydrin in an alkaline medium or in the presence of an acid catalyst , which is subsequently treated with alkali.

Glycidyl ethers of this type are formed, for example, by acyclic alcohols, for example, ethylene glycol, diethylene glycol or higher poly (hydroxyethylene) glycols, propane-1,2-diol or poly (hydroxypropylene) glycols, propane-1,3-diol, butane-1 , 4-diol, poly (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol or sorbitol , and polyepichlorohydrins. Additional glycidyl ethers of this type are formed by cycloaliphatic alcohols, such as 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane, or alcohols that contain aromatic groups and / or additional functional groups such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.

Glycidyl ethers can also be based on monatomic phenols, such as, for example, p-tert-butylphenol, resorcinol or hydroquinone, or on polyatomic phenols, such as, for example, bis (4-hydroxyphenyl) methane, 4,4'-dihydroxybiphenyl bis (4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4 -hydroxyphenyl) propane.

Other suitable hydroxy compounds for preparing glycidyl ethers are novolac resins obtained by condensation of aldehydes such as formaldehyde, acetaldehyde, chloral or furfuraldehyde with phenols or bisphenols, which are unsubstituted or substituted with chlorine atoms or C ₁ -C ₉ alkyl groups for example phenol, 4-chlorophenol, 2-methylphenol or 4-tert-butylphenol.

III) Poly (N-glycidyl) compounds obtained by dehydrochlorination of the products of the interaction of epichlorohydrin with amines that contain at least two amine hydrogen atoms. These amines are, for example, aniline, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane.

Poly (N-glycidyl) compounds also include triglycidyl isocyanurate, N, N'-glycidyl derivatives of cycloalkylene ureas, such as ethylene urea or 1,3-propylene urea, and diglycidyl derivatives of hydantoins, such as 5,5-dimethyl hydantoin.

IV) Poly (S-glycidyl) compounds, for example, di-S-glycidyl derivatives, which are formed by dithiols, such as, for example, ethane-1,2-dithiol, or bis (4-mercaptomethylphenyl) ether.

V) Cycloaliphatic epoxies such as, for example, bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane or 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate.

Epoxy resins in which 1,2-epoxy groups are attached to various heteroatoms or functional groups can also be used. These compounds include, for example, N, N, O-triglycidyl derivative of 4-aminophenol, glycidyl ether-glycidyl ester of salicylic acid, N -glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin or 2-glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoin-3-yl) propane.

Particularly preferred are those indicated in paragraphs I and II, and most preferred are those indicated in paragraph II.

The monohydric alcohol and / or polyhydric alcohol (polyol) used in the epoxy resin composition of the present invention preferably has an average nominal hydroxyl functionality of 1-8 and an average molecular weight of 32-8000. Mixtures of monohydric and / or polyhydric alcohols may also be used.

Examples of these monohydric alcohols are methanol, ethanol, propanol, butanol, phenol, cyclohexanol and hydrocarbon monohydric alcohols having an average molecular weight of 200-5000, such as aliphatic and polyether monohydric alcohols. Examples of polyhydric alcohols are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, sorbitol, sucrose, glycerol, ethanediol, propanediol, butanediol, pentanediol, carbon atoms or more, aromatic polyols, aromatic compounds, aromatic compounds, aromatic compounds and aromatic compounds and having a molecular weight of up to 8000, polyester polyols having an average molecular weight of 200-8000, polyether polyester polyols having an average molecular weight of SSU 200-8000, and simple polyether polyols having an average molecular weight of 200-8000. These monohydric alcohols and polyols are commercially available. Suitable examples are Daltocel F526, Daltocel F555 and Daltocel F442, which are all simple polyether triols from Huntsman, Voranol P400 and Alcupol R1610, which are simple polyether polyols from DOW, and Repsol, respectively, and Priplast 1838 and 3196, which are high molecular weight polyester polyols from Croda, and Capa 2043 polyol, linear mid-MW polyester diol of about 400 from Perstorp, and K-flex polyols 188 and A308, which are polyester polyols, from King Industries having MW of about 500 and 430, respectively , aromatic polyester polyols of type Stepanpol PH56 and BC180, having average molecular weights of about 2000 and 600, respectively, and Neodol 23B, which is an aliphatic monohydric alcohol, from Shell.

Most preferred are polyols based on esters and ethers having an average molecular weight of 200-6000 and an average nominal functionality of 2-4.

A compound comprising a carboxamide group (also hereinafter referred to as a “carboxamide” compound) is preferably selected from compounds of the formula NH ₂ —CO — R, where R is 1) a hydrogen atom (—H), 2) —NR ₁ R ₂ , 3 ) hydrocarbyl containing 1-20 carbon atoms and optionally including hydroxy groups, ether groups, a halogen atom and amine groups, or 4) -R ₃ CO-NH ₂ , where R ₁ and R _{2 are} independently selected from a hydrogen atom, hydroxy groups, a halogen atom and hydrocarbyl groups, where the hydrocarbyl groups contain 1-10 carbon atoms and n necessarily include hydroxy, etherified hydroxy group, a halogen atom and / or amine groups and wherein R ₁ is a divalent hydrocarbon radical containing up to 8 carbon atoms. Mixtures of these carboxamide compounds may also be used. Preferably, these carboxamides have a molecular weight of not more than 499.

The hydrocarbyl groups in these carboxamides may be linear or branched, saturated or unsaturated and cyclic or non-cyclic, they may be aliphatic, aromatic or araliphatic.

More preferred carboxamides are those in which R is 1) —NHR ₁ R ₂ , 2) alkyl containing 1-10 carbon atoms and optionally including 1-3 hydroxy and / or ether groups, 3) phenyl or 4) tolyl, where R ₁ and R _{2 are} independently selected from a hydrogen atom, hydroxy group, phenyl, tolyl and alkyl containing 1-6 carbon atoms and optionally including hydroxy and / or ether groups. Mixtures of these more preferred compounds are also more preferred.

Examples of very useful carboxamide compounds are for the formula NH ₂ —CO — R, where R is as defined below.

R Title -NH ₂ Urea -NHOH Hydroxyurea -NH (CH ₃ ) N-methylurea -N (CH ₃ ) ₂ 1,1-dimethylurea -N (C ₂ H ₅ ) ₂ 1,1-diethylurea -NH-C ₆ H ₅ Phenylurea -NH-C ₆ H ₄ -CH ₃ Tolylurea -H Formamide -CH ₃ Ethanamide -C ₂ H ₅ Propionamide -OC ₂ H ₅ Ethyl carbamate -OC ₄ H ₉ Butylcarbamate -OC ₆ H ₅ Phenylcarbamate -OCH ₂ -CH ₂ OH Hydroxyethyl carbamate -OCH (CH ₃ ) -CH ₂ OH Hydroxypropylcarbamate -CH (CH ₃ ) -OH Lactamide -C ₆ H ₅ Benzamide

Nicotinamide

Most preferably, urea is used. It should be noted that when calculating the number of carboxamide equivalents, it is assumed that urea contains 2 carboxamide groups.

In order to obtain an epoxy resin composition according to the present invention, the aforementioned carboxamide compound is combined and mixed with the aforementioned monohydroxy alcohol and / or polyol, preferably at ambient pressure and a temperature between 10 ° C. and 120 ° C. Although special mixing operations may be used, conventional mixing is sufficient. The mixture thus obtained can optionally be cooled if it is mixed at elevated temperature; then it is mixed with the above epoxy resin, preferably at ambient pressure and a temperature between 10 ° C. and 120 ° C. The relative amounts of epoxy resin, polyol and carboxamide compound are selected so as to correspond to the aforementioned hydroxy / epoxy and carboxamide / epoxy ratios.

The polyisocyanate used to prepare the polyisocyanate composition of the present invention may be selected from aliphatic and preferably aromatic polyisocyanates. Preferred aliphatic polyisocyanates are hexamethylene diisocyanate, isophorone diisocyanate, metilenditsiklogeksildiizotsianat and cyclohexane diisocyanate and preferred aromatic polyisocyanates are toluene diisocyanate, naphthalene diisocyanate, tetramethylxylene diisocyanate, phenylene diisocyanate, tolidindiizotsianat and especially methylene (MDI) and compositions based on polyisocyanate comprising methylene (so-called polymeric MDI, crude MDI modified with uretonimine MDI and f rpolimery containing free isocyanate groups formed MDI, and polyisocyanates comprising MDI), and mixtures of these polyisocyanates. MDI and compositions comprising MDI are most preferred, especially those selected from 1) diphenylmethanediisocyanate containing at least 35%, preferably at least 60% by weight of 4,4'-diphenylmethanediisocyanate (4,4'-MDI ); 2) modified with carbodiimide and / or uretonimine, a variant of the polyisocyanate 1), a variant having an NCO number of 20% by weight or more; 3) a urethane-modified variant of polyisocyanate 1) and / or 2); a variant having an NCO number of 20% by mass or more and which is the product of the interaction of an excess of 1) and / or 2) polyisocyanate and a polyol having an average nominal hydroxyl functionality of 2-4 and an average molecular weight of at least 1000; 4) diphenylmethanediisocyanate, including a homolog containing 3 or more isocyanate groups; 5) prepolymers having an NCO number of 5-30% by weight and being the product of the interaction of any one or more polyisocyanates 1) -4) and a polyol having an average nominal hydroxyl functionality of 2-4 and an average molecular weight of more than 1000 and up to 8000; and 6) mixtures of any of the above polyisocyanates.

Polyisocyanate 1) comprises at least 35% by weight of 4.4'-MDI. These polyisocyanates are known in the art and include pure 4,4'-MDI and isomeric mixtures of 4,4'-MDI, 2,4'-MDI and 2,2'-MDI. It should be noted that the amount of 2,2'-MDI in isomeric mixtures is the level of impurities and, in general, does not exceed 2% by weight, and the rest is 4,4'-MDI and 2,4'-MDI. Polyisocyanates, like these, are known in the art and are commercially available, for example, Suprasec® MPR and 1306 from Huntsman. (Suprasec is a trademark of Huntsman Corporation or its subsidiary, which is registered in one or more, but not in all countries).

Modified carbodiimide and / or uretonimine variants of the above polyisocyanate 1) are also known in the art and are commercially available; e.g. Suprasec® 2020 from Huntsman. Urethane-modified variants of the above 1) polyisocyanate are also known in the art, see, for example, The ICI Polyurethanes Book, G. Woods, 1990, 2 ^nd edition, pages 32-35.

Polyisocyanate 4) is also widely known and commercially available. These polyisocyanates are often referred to as crude MDI or polymer MDI. Examples are Suprasec® 2185, Suprasec® 5025 and Suprasec® DNR from Huntsman.

Prepolymers (polyisocyanate 5)) are also widely known and commercially available. Examples are Suprasec® 2054 and Suprasec® 2061, both from Huntsman.

Mixtures of the aforementioned polyisocyanates can also be used, see, for example, The ICI Polyurethanes Book, G. Woods, 1990, 2 ^nd edition, pages 32-35. An example of this commercially available polyisocyanate is Suprasec® 2021 from Huntsman.

The lithium halide used in the polyisocyanate composition used in accordance with the present invention is used in an amount of 0.0001-0.04 and preferably 0.00015-0.025 and most preferably 0.0005-0.02 moles per equivalent of isocyanate and preferably selected from lithium chloride and lithium bromide. Most preferred is lithium chloride.

The urea compound used in the polyisocyanate composition used in accordance with the present invention is used in such an amount that the number of urea + biuret equivalents is 0.0001-0.4, and preferably 0.001-0.2, and most preferably 0.001-0. 05 to the equivalent of isocyanate. Most preferably, the number of equivalents of urea + biuret in the urea compound in the polyisocyanate-based composition per mole of lithium halide is in the range from 0.5 to 60 and most preferably from 0.5 to 30. The urea compound should not include other isocyanate-reactive groups ( i.e. different from urea groups). When calculating the number of urea equivalents, the urea groups in the carboxamide compound having a molecular weight of at least 499 are not taken into account.

The urea compound used in the polyisocyanate composition used in accordance with the present invention has an average molecular weight of 500-15000 and preferably 600-10000 and most preferably 800-8000. This urea compound is prepared by the reaction of polyisocyanates and amines.

The polyisocyanates used to prepare this urea compound may be selected from the polyisocyanates mentioned above. The preferences mentioned above also apply here. Most preferably, polyisocyanates 1) and 2) and mixtures thereof are used. The polyisocyanate used to make the polyisocyanate composition of the present invention and the polyisocyanate used to make the urea compound may be the same or different.

The amines used to prepare the urea compounds may be monoamines or polyamines. Monoamines are preferably used, optionally including a small amount of polyamines. The average functionality of the amine in these mixtures is preferably not more than 1.2. Most preferably, only monoamines are used. These amines are preferably primary amines.

The molecular weight of the amines is selected so that immediately after interaction with the selected polyisocyanate, the molecular weight of the obtained urea compound falls into the above ranges. In general, the molecular weight of amines ranges from 200 to 7500, and preferably from 200 to 4500, and most preferably from 200 to 3000.

Amines can be selected from those known in the art, such as amine-terminated hydrocarbons, polyesters, polyethers, polycaprolactones, polycarbonates, polyamides and mixtures thereof. Most preferred are amine-terminated polyoxaalkylene monoamines and, in particular, polyoxyethylene-polyoxypropylene monoamines. Preferably, the oxypropylene content of these polyoxyalkylene monoamines is at least 50 and preferably at least 75% by weight based on the total weight of the monoamine molecule. Preferably, the polyoxyalkylene monoamines contain a monoalkyl group at either end of the polymer chain, the alkyl group contains 1-8 and preferably 1-4 carbon atoms. These monoamines are known in the art. They were obtained by alkoxylation of an alkyl monoalcohol containing 1-8 carbon atoms, and the subsequent conversion of a polyoxyalkylated monohydric alcohol to a monoamine. These monoamines are commercially available. Examples are Jeffamine® M-600 and M-2005, both from Huntsman (Jeffamine is a trademark of Huntsman Corporation or its subsidiary registered in one or more, but not all countries). Mixtures of monoamines may also be used.

In light of the foregoing, the most preferred urea compound used in the polyisocyanate composition used in accordance with the present invention is a urea compound obtained by the reaction of methylene diphenyl diisocyanate or a polyisocyanate comprising methylene diphenyl diisocyanate or a mixture of these polyisocyanates and a polyoxyalkylene monoamine, including an oxyl group including at least 75% by weight, based on the total weight of the monoamine molecules, and having an average molecular weight a mass of 200-3000, and where the amine is a primary amine.

The polyisocyanate and monoamine are combined and mixed and allow them to interact. The reaction is exothermic and therefore does not require heating and / or a catalyst, although heat and / or a catalyst can be used if it is considered convenient. For example, it may be convenient to pre-heat the polyisocyanate and / or monoamine to 40-60 ° C, and then mix them. After mixing, the temperature of the reaction mixture is preferably kept below 90 ° C. in order to avoid side reactions, such as biuret formation. To ensure that the entire amine interacts, a slight excess of polyisocyanate can be used, and therefore, carrying out the reaction at an index of 101-110 is preferred. After no more than 1 hour, the reaction can be considered complete and the urea compound is ready for use to obtain the polyisocyanate composition used according to the present invention.

Since a small excess of polyisocyanate is used in the preparation of the urea compound, and since the urea compound in the next step is added to a relatively large amount of polyisocyanate, some urea groups can turn into biuret groups. By controlling the reaction temperature and the temperature of the subsequent mixing stage, such biuret formation can be avoided as much as possible. In general, the number of urea groups that are converted to biuret groups is less than 25% and preferably less than 10%.

The polyisocyanate composition used according to the present invention is prepared by mixing the polyisocyanate, the urea compound and lithium halide in any order at ambient conditions or at elevated temperature, for example, at 40-70 ° C. Preferably, lithium halide is pre-mixed with the urea compound and this mixture is then added to the polyisocyanate and mixed. Before mixing lithium halide and a urea compound, it may be convenient to dissolve lithium halide in a solvent, such as an organic solvent such as an alcohol, for example methanol or ethanol. Dissolved lithium halide is then added to the urea compound. Then the solvent can be distilled off if desired. Pre-mixing and mixing is carried out at ambient conditions or at elevated temperature, for example, at 40-70 ° C, and using normal mixing. The relative amounts of polyisocyanate, urea and lithium halide compounds are selected so that the final polyisocyanate-based composition used according to the present invention has the same relative amounts of isocyanate groups, urea groups and lithium halide as previously discussed. Not wanting to be bound by any theory, the inventors believe that lithium halide is present in dissociated form, in the form of a complex with urea groups, as the so-called bidentate complex.

A polyisocyanate composition is used to prepare a curable composition of the present invention by combining and mixing an epoxy resin composition and a polyisocyanate composition in such relative quantities that the number of epoxy equivalents per isocyanate equivalent is in the range of 0.003-1 and preferably 0.003-0.5 and most preferably 0.005-0.25. These compositions are preferably combined and mixed under ambient conditions. The relative amounts of the ingredients are selected to provide a cure composition index of 300-100000, and preferably 500-10000.

The curable composition thus obtained has good environmental stability. It is used to obtain a polyurethane-polyisocyanurate material, providing interaction at elevated temperatures. Therefore, the invention also relates to a polyurethane-polyisocyanurate material obtained from the interaction of the curable composition of the present invention and a polyurethane-polyisocyanurate material obtained from the interaction of the curable composition of the present invention at an elevated temperature, and to a method for producing these polyurethane-polyisocyanurate materials based on the interaction of the curable composition of the present invention at elevated temperature. Preferably, the reaction is carried out at an index of 300-100000, and most preferably 500-10000. Preferably heat is applied to bring the curable composition to a temperature above 50 ° C and preferably above about 80 ° C. The curable composition can then quickly solidify (the so-called rapid cure) while the temperature rises further (the reaction is exothermic).

Before curing, the curable composition can be fed into the mold to give it a specific shape, or into the cavity of the object to provide an object with an internal part of polyurethane-polyisocyanurate, or on the surface to obtain such a surface from a polyurethane-polyisocyanurate layer, or it can be used to repair an object, and in particular a pipe, by applying it to the inner and / or outer surface of a given object or such pipe (examples of the repair of such a pipe are described in US Pat. Nos. 4,090,663, 4,366,012 and 4,621,296) or it can be used to bind materials, as disclosed in WO 2007/096216.

Before the curable composition hardens, additives or its components can be added to it. Examples of additives are other catalysts, blowing agents, surfactants, water absorbers, such as alkyl orthoformate and, in particular, triisopropyl orthoformate, antimicrobial agents, flame retardants, smoke suppressants, UV stabilizers, coloring agents, plasticizers, agents that facilitate the removal of press products -forms, rheological modifiers, wetting agents, dispersants and fillers.

If desired, the polyurethane-polyisocyanurate material of the present invention may be post-cured.

The invention is illustrated by the following examples.

Examples

Chemicals used

Jeffamine M-600: A polyoxyethylene polyoxypropylene monofunctional primary amine having a molecular weight of approximately 560 and an oxypropylene / hydroxyethylene ratio of approximately 9/1, available from Huntsman. In these examples, it is called the M-600.

Huntsman Suprasec 1306 Polyisocyanate: 4.4'-MDI. These examples are called S1306.

Suprasec 2020 Polyisocyanate: A uretonimine-modified polyisocyanate from Huntsman, referred to as S2020 in these examples.

Alcupol R1610 polyol from Repsol referred to in this document R1610; polyoxypropylene triol having an average molecular weight of approximately 1050.

Daltocel F526 represents polyoxyethylene triol from Huntsman; MW is approximately 1300. Daltocel is a trademark of Huntsman Corporation or its subsidiaries and is registered in one or more, but not all countries. Daltocel F442 and Daltocel F555 are also Huntsman polyether polyols having a nominal functionality of 3 and an average molecular weight of approximately 4,000 and 6,000, respectively.

Voranol P400 Polyol from DOW; polyoxypropylenediol having an average molecular weight of approximately 430.

Carbalink HPC: Hydroxypropylcarbamate, Huntsman Carboxamide Compound

Huntsman's Araldite DY-T Epoxy, trimethylolpropane triglycidyl ether, referred to herein as DY-I. Araldite and Carbalink are trademarks of Huntsman Corporation or its subsidiaries and are registered in one or more, but not all countries.

In none of the following examples, biuret formation was observed.

Example 1

Obtaining compositions based on polyisocyanate, including lithium chloride and a urea compound.

The number of moles of amine, which was maintained at 50 ° C, and the number of moles of polyisocyanate 1, which was also maintained at 50 ° C, were mixed and allowed to interact for 1 hour with stirring to form a urea compound. The reaction temperature was maintained at 80 ° C. The amount of salt was dissolved in the amount of ethanol with stirring.

This solution was added to the urea compound obtained above, which was still maintained at 80 ° C. Stirring was continued for approximately 15 minutes. A significant amount of ethanol was distilled off by distillation at 85-95 ° C. The amount of urea / salt mixture thus obtained is shown below in Table 1 together with the amounts used and the type of amine, polyisocyanate 1 and salt and the amount of ethanol used.

An amount of the urea / salt mixture thus obtained (having a temperature of approximately 60 ° C.) was added to the amount of polyisocyanate 2 and mixed to obtain a polyisocyanate composition for use with an epoxy resin composition.

Table 2 below shows the quantities and types of ingredients used, together with the ratio of the number of equivalents of urea + biuret per equivalent of isocyanate and the number of moles of salt per equivalent of isocyanate and the number of equivalents of urea + biuret per mole of salt. Parts by weight are indicated in parts by weight.

Table 1 Urea Compounds Amine Type /
quantity in moles Type of polyisocyanate 1 / amount in moles Type of salt /
amount in grams Ethanol /
amount in grams A mixture of urea + salt /
amount in grams A M-600/2 S1306 / 1.04 LiCl / 23.9 125.3 1407.6 B M-600/2 S1306 / 1.04 LiCl / 100.7 528.5 1484.4 C M-600/2 S1306 / 1.04 LiCl / 48.6 255.0 1432.3 D M-600/2 S1306 / 1.04 LiCl / 11.8 62.1 1396.0

table 2 Mixtures of Polyisocyanates The urea compound from table 1 /
amount in parts by weight Type of polyisocyanate 2 /
amount in parts by weight Urea + biuret /
NCO ratio Salt / NCO ratio Urea + biuret / salt ratio one A / 5 S2020 / 95 0,0109 0.003 3.65 2 B / 1.25 S2020 / 95 0.0027 0.003 0.91 3 C / 2.5 S2020 / 95 0.0055 0.003 1.82 four A / 2.5 S2020 / 95 0.0055 0.0015 3.65 5 A / 15 S2020 / 95 0,0328 0.009 3.65 6 A / 1.25 S2020 / 95 0.0027 0,0007 3.65 7 D / 10 S2020 / 95 0,0219 0.003 7.30

Obtaining compositions based on epoxy resin of the present invention

The carboxamide compound was added to polyol 1 and stirred at ambient pressure and at 120 ° C. for 1 hour. Then polyol 2 was added if a second polyol was used. After the mixture was cooled to ambient conditions, Araldite DY-T was added and mixed under ambient conditions. The amounts and types of ingredients used are presented in Table 3, which also shows OH / epoxide and carboxamide / epoxide equivalent ratios.

Obtaining curable compositions and polyisocyanurate materials of the present invention

The compositions of Table 2 were mixed with the epoxy compositions of the present invention (and comparative examples) for 30 seconds and left at room temperature to determine shelf life by evaluating the temperature profile of a thermocouple placed in a liquid resin before the temperature started to rise. The curable composition was allowed to react to produce the polyurethane-polyisocyanurate materials of the present invention. The presence of isocyanurate groups was confirmed by FTIRS (FTIRS).

The ingredients used, the amount in parts by weight, the number of epoxy equivalents per equivalent of isocyanate and the shelf life are presented in table 3.

In the first column, A1 means that the urea compound A (table 1) and polyisocyanate-based mixture 1 (table 2) were used, and A6 means that the urea compound and polyisocyanate mixture 6 were used. For B2, 9 different experiments were carried out with a urea compound B and a mixture of 2 polyisocyanates.

Table 3 Curable Compositions The composition of Table 2 /
amount in parts by weight Type of Epoxide /
amount in parts by weight Type of polyol 1 /
amount in parts by weight Type of polyol 2 /
amount in parts by weight Type of carboxamide /
amount in parts by weight Epoxy ratio
Nco OH / epoxy ratio The ratio of carboxamide /
epoxy Shelf life (h) A1-1 * 1/100 DY-T / 4 F526 / 2 P400 / 5 n.u. 0,048 0.87 0,000 5 A1-2 1/100 DY-T / 4 F526 / 2 P400 / 5 Urea / 0.02 0,048 0.87 0,021 45 A1-3 1/100 DY-T / 4 F526 / 2 P400 / 5 Urea / 0.04 0,048 0.87 0,042 91 A1-4 1/100 DY-T / 4 F526 / 2 P400 / 5 Urea / 0.1 0,048 1,08 0.104 312 B2-1 * 2 / 96.25 DY-T / 4 F526 / 2 P400 / 5 n.u. 0,048 0.87 0,000 3 B2-2 2 / 96.25 DY-T / 4 F526 / 2 P400 / 5 Urea / 0.02 0,048 0.87 0,021 5 B2-3 2 / 96.25 DY-T / 4 F526 / 2 P400 / 5 Urea / 0.04 0,048 0.87 0,042 9 B2-4 2 / 96.25 DY-T / 4 F526 / 5 P400 / 5 Urea / 0.10 0,048 1,08 0.104 89 B2-5 * 2 / 96.25 DY-T / 4 F442 / 5 P400 / 5 n.u. 0,048 0.84 0,000 5 B2-6 2 / 96.25 DY-T / 4 F442 / 5 P400 / 5 N-methylurea / 0.010 0,048 0.84 0.004 6 B2-7 2 / 96.25 DY-T / 4 F442 / 5 P400 / 5 N-methylurea / 0.020 0,048 0.84 0.008 7 B2-8 2 / 96.25 DY-T / 4 F442 / 5 P400 / 5 N-methylurea / 0.050 0,048 0.84 0,021 fourteen B2-9 2 / 96.25 DY-T / 4 F442 / 5 P400 / 5 N-methylurea / 0.10 0,048 0.84 0,042 35 C3-1 3 / 97.5 DY-T / 4 F442 / 5 P400 / 5 1,1-diethylurea / 0.010 0,048 0.84 0.003 7 C3-2 3 / 97.5 DY-T / 4 F442 / 5 P400 / 5 1,1-diethylurea / 0.020 0,048 0.84 0.005 9 C3-3 3 / 97.5 DY-T / 4 F442 / 5 P400 / 5 1,1-diethylurea / 0.050 0,048 0.84 0.013 fourteen C3-4 3 / 97.5 DY-T / 4 F442 / 5 P400 / 5 1,1-diethylurea / 0.10 0,048 0.84 0,027 24 A1-5 1/100 DY-T / 4 F526 / 5 R1610 / 10 Propionamide / 0.05 0,048 1.24 0,021 90 A1-6 1/100 DY-T / 4 F526 / 5 R1610 / 10 Propionamide / 0.13 0,048 1.24 0,053 130 A1-7 1/100 DY-T / 4 F526 / 5 R1610 / 10 Propionamide / 0.25 0,048 1.24 0.107 180 A4-1 4 / 97.5 DY-T / 4 F526 / 5 R1610 / 10 Propionamide / 0.25 0,048 1.24 0.107 > 138 A1-8 1/100 DY-T / 4 F555 / 5 n.u. Tolylurea / 0.010 0,048 0.08 0.002 12 A1-9 1/100 DY-T / 4 F555 / 5 n.u. Tolylurea / 0.05 0,048 0.08 0.010 41 A1-10 1/100 DY-T / 4 R1610 / 15 n.u. Carbalink HPC / 0.13 0,048 1.34 0,034 thirty A4-2 4 / 97.5 DY-T / 4 R1610 / 15 n.u. Carbalink HPC / 0.13 0,048 1.34 0,034 55 A1-11 1/100 DY-T / 4 F526 / 0.25 R1610 / 5 Urea / 0.0063 0,048 0.46 0.007 25 A1-12 1/100 DY-T / 8 F526 / 2.5 R1610 / 5 Urea / 0.063 0,096 0.31 0,033 97 A1-13 1/100 DY-T / 12 F526 / 2.5 R1610 / 5 Urea / 0.063 0.014 0.21 0,022 40 A5-1 5/110 DY-T / 4 F526 / 2.5 R1610 / 10 Urea / 0.063 0,048 1,07 0,065 150 A4-3 4 / 97.5 DY-T / 4 R1610 / 15 n.u. Carbalink HPC / 0,033 0,048 1.34 0.009 fourteen A1-15 1/100 DY-T / 1.5 F526 / 1.5 n.u. Urea / 0.015 0.018 0.28 0,042 > 65 D7-1 7/105 DY-T / 4 F526 / 1 P400 / 5 Urea / 0.010 0,048 0.79 0.010 > 65 nu means not used
* Comparative example

Additional examples of the invention

Table 4 provides information related to several additional experiments similar to Table 3, except that T _{g of} polyisocyanurate was given instead of the cure time of the curable composition. T _{g was} measured by differential mechanical thermal analysis on samples having a thickness of approximately 4 mm, which were cured in an open mold for 1 hour at 125 ° C in a thermostat. With additional subsequent curing, T _g may be increased.

Table 4 Curable Compositions The composition of Table 2 /
amount in parts by weight Type of Epoxide /
amount in parts by weight Type of polyol 1 / amount in parts by weight Type polyol 2 / amount in parts by weight Type of carboxamide /
amount in parts by weight Epoxy ratio
Nco OH / epoxy ratio Carboxamide / epoxy ratio T _g (tan δ), ° C A4-4 4 / 97.5 DY-T / 4 F526 / 2.5 R1610 / 12.5 Urea / 0.13 0,048 1.29 0.130 183.9 A1-14 1/100 DY-T / 4 F526 / 2.5 R1610 / 12.5 Urea / 0.063 0,048 1.29 0,065 192.0 A6-1 6 / 96.25 DY-T / 4 F526 / 2.5 R1610 / 12.5 Urea / 0.13 0,048 1.29 0.130 186.8 A1-7 1/100 DY-T / 4 F526 / 5 R1610 / 10 Propionamide / 0.25 0,048 1.24 0.107 213.1 ⁽¹⁾ A1-10 1/100 DY-T / 4 R1610 / 15 n.u. Carbalink HPC / 0.13 0,048 1.34 0,034 221.7 ⁽¹⁾ A1-5 1/100 DY-T / 4 F526 / 5 R1610 / 10 Propionamide / 0.050 0,048 1.24 0,021 239.6 B2-10 2 / 96.25 DY-T / 4 F526 / 5 P400 / 5 N-methylurea / 0.25 0,048 1,08 0.105 183.4 A1-16 1/100 DY-T / 4 F526 / 1 R1610 / 14 1,1-diethylurea / 0.25 0,048 1.32 0.007 194.3 A1-17 1/100 DY-T / 8 F526 / 1.5 R1610 / 13.5 Urea / 0.038 0,096 0.65 0,020 197.8 ⁽¹⁾ Cured for 1 hour at 150 ° C
nu means not used

Claims (15)

1. An epoxy resin composition for producing a curable composition comprising a polyisocyanate comprising an epoxy resin, a polyol and a carboxamide compound, wherein
- the carboxamide compound has the structure NH ₂ —CO — R, where R is 1) —NR ₁ R ₂ , 2) alkyl containing 1-10 carbon atoms and optionally including 1-3 hydroxyl and / or ether groups, 3) phenyl or 4) tolyl, where R ₁ and R _{2 are} independently selected from a hydrogen atom, hydroxy, phenyl, tolyl and alkyl containing 1-6 carbon atoms and optionally including a hydroxy and / or ether group, and mixtures of these compounds , and
- where the number of hydroxyl equivalents per equivalent of epoxide is 0.02-100 and preferably 0.03-50 and most preferably 0.05-10, and the number of carboxamide equivalents per equivalent of epoxide is 0.0005-1 and preferably 0.005-0.7 and most preferably 0.01-0.5. 2. The composition according to claim 1, where the polyol has an average nominal functionality of 1-8 and an average molecular weight of 32-8000 and where the number of hydroxyl equivalents per equivalent of epoxide is 0.05-10. 3. The composition according to one of claims 1 and 2, where the number of carboxamide equivalents per epoxide equivalent is 0.01-0.5. 4. A method of obtaining a composition according to one of claims 1 to 3, where a mixture of a polyol and a carboxamide compound is combined and mixed with an epoxy resin. 5. A curable composition for producing a polyurethane-polyisocyanurate material obtained by combining and mixing an aromatic polyisocyanate-based composition comprising a polyisocyanate, lithium halide and a urea compound having an average molecular weight of 500-15000 and optionally including biuret groups and epoxy resin compositions according to claims 1-3, where the number of moles of lithium halide per equivalent of isocyanate lies in the range of 0.0001-0.04 and the number of equivalents of urea + biuret per equivalent of isocyanate lies in the range of 0.0 001-0.4, and the number of equivalents of epoxide per equivalent of isocyanate lies in the range of 0.003-1. 6. The composition according to claim 5, where the urea compound does not include other isocyanate-reactive groups except urea groups, and where the number of urea + biuret equivalents per isocyanate equivalent is 0.001-0.2, and where the urea compound is obtained by the reaction of methylene diphenyl diisocyanate and polyisocyanate comprising methylene diphenyl diisocyanate, or a mixture of these polyisocyanates with polyoxyalkylene monoamine including hydroxypropylene groups in an amount of at least 50% by weight based on the total weight of the monoamine molecules and having an average a molecular weight of 200-3000, and where the amine is the primary amine and where the number of equivalents of urea + biuret per mole of lithium halide is 0.5-60. 7. The composition according to one of claims 5 and 6, wherein the polyisocyanate is methylene diphenyl diisocyanate or a polyisocyanate-based composition comprising methylene diphenyl diisocyanate or a mixture of these polyisocyanates. 8. The composition according to one of paragraphs.5 and 6, where the amount of lithium halide is 0.00015-0.025 moles per equivalent of isocyanate. 9. The composition according to one of paragraphs.5 and 6, where the lithium halide is lithium chloride. 10. The composition according to one of paragraphs.5 and 6, where the epoxy resin is liquid at 20-25 ° C. 11. A method for producing a curable composition according to one of claims 5 to 10 by combining and mixing the polyisocyanate-based composition described in claim 6 and the epoxy-based composition described in claim 6, the amount of the epoxy-based composition is such that the number of equivalents of epoxide per equivalent of isocyanate lies in the range of 0.003-1. 12. Polyurethane-polyisocyanurate material obtained by the interaction of the curable composition according to one of claims 5 to 10 at an elevated temperature. 13. Polyurethane-polyisocyanurate material obtained by the interaction of the curable composition according to claims 5-10 at an elevated temperature. 14. A method of obtaining a polyurethane-polyisocyanurate material according to one of claims 12 and 13, based on the interaction of the curable composition according to one of claims 5 to 10 at an elevated temperature. 15. The use of a carboxamide compound having the structure NH ₂ —CO — R, where R is 1) —NR ₁ R ₂ , 2) alkyl containing 1-10 carbon atoms and optionally including 1-3 hydroxyl and / or ether groups, 3) phenyl or 4) tolyl, where R ₁ and R _{2 are} independently selected from a hydrogen atom, hydroxy, phenyl, tolyl and alkyl containing 1-6 carbon atoms and optionally including a hydroxy and / or ether group, and mixtures of these compounds to improve the shelf life of the curable polyisocyanine-based composition that one.